CN1646590A - Polyurethane resin based slush molding material - Google Patents
Polyurethane resin based slush molding material Download PDFInfo
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- CN1646590A CN1646590A CNA038081083A CN03808108A CN1646590A CN 1646590 A CN1646590 A CN 1646590A CN A038081083 A CNA038081083 A CN A038081083A CN 03808108 A CN03808108 A CN 03808108A CN 1646590 A CN1646590 A CN 1646590A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
- B60K37/00—Dashboards
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
- C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/18—Slush casting, i.e. pouring moulding material into a hollow mould with excess material being poured off
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2140/00—Compositions for moulding powders
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Combustion & Propulsion (AREA)
- Transportation (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A slush molding material which comprises a polyurethane resin (A) exhibiting a difference between a softening starting temperature and a softening completion temperature as measured by the thermomechanical analysis penetration method of 0 to 30 DEG C and a softening starting temperature of 135 to 200 DEG C, wherein the resin (A) has a hard segment comprising a diisocyanate having a symmetrical structure and a low molecular weight diamine having a symmetrical structure and/or a low molecular weight diol and having a number average molecular weight of 200 to 2000 in a content of 5 to 50 wt %, and has a soft segment comprising a high molecular weight diol having a number average molecular weight of 500 to 5,000, has an aromatic ring content of 35 wt % or less, and has an aromatic ring content of x and a urea group content of y satisfying the formula: -0.1x + 2.5 <= y <= -0.1x + 6. The slush molding material exhibits improved melting property in slush molding and also is excellent in thermal resistance.
Description
Technical field
The present invention relates to a kind of material that is used for slush molding, especially a kind of slush molding material that is used for automotive interior.
Background technology
In the past, for the adhesion property of improving lining cloth, water-fast washing and the dry cleaning resistance energy, a kind of hot melt adhesive that contains TPU(Thermoplastic polyurethanes) has been proposed, it adopts initial softening temperature that thermomechanical analysis infiltration side measures and the difference between the end softening temperature and initial softening temperature to remain in the specific scope, and described hot melt adhesive also is used as the material of slush molding.(for example, see Japanese Patent No.2984921.)
Yet, for the material that is used for slush molding, especially be suitable for the material of automotive interior, wish that it can satisfy such as the moulding material that can obtain to have excellent heat resistance and outward appearance and has condition such as wear resistance.Be conceived under the situation of polyurethane-based material, do not find to satisfy the slush molding material of these characteristics as yet.
On the other hand, for positioned inside the instrument panel of air bag is arranged, be provided with tear line at the door part of air bag, described tear line is used for opening when needed air bag.Although in traditional panel, described tear line is positioned on the front surface and rear surface of panel enclosure, with convenient the door part of common panel is opened, but when being positioned at design surface outside, it will lose aesthetic property, therefore instrument panel usually integrally is designed to have an air bag door part, described door part for example only is provided with tear line at the back on surface, thereby avoids tear line is exposed to design surface.
Yet, if the soft PVC class powdered material that uses in the conventional panel is applied to instrument panel, because the effusion gradually of softening agent, causes resin to become fragile and shrinks, therefore when air bag expanded, tear line part in addition also can be split.In order to address this problem, a kind of crosslinked TPU(Thermoplastic polyurethanes) material (for example, the spy opens 2001-40056) has been proposed.But such scheme seems and can not address this problem fully.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of material that is used for slush molding, described material has the melting characteristic of improvement in the slush molding process, and has excellent thermotolerance.
The present invention also aims to+provide a kind of slush molding material, described material can be under service condition widely, when air bag expands, make to tear and mouthful split along tear line, described material is suitable for surface forming, and can split at other positions hardly, in the instrument panel that integrally has an air bag opening portion, can not be exposed on the design surface by the so molded tear line that makes.
In other words, the invention provides a kind of material that is used for slush molding, wherein contain TPU(Thermoplastic polyurethanes) (A) (below be called resin (A)), in 0 to 30 ℃ of scope, wherein Sti is in 135～200 ℃ scope for initial softening temperature that described resin (A) is measured according to thermomechanical analysis infiltration side and the difference between the end softening temperature (following Sti and the Ste of being abbreviated as respectively) (below be abbreviated as Δ ST).Resin (A) optimization polyurethane resin, described urethane resin contains hard segment (A1) and soft chain segment (A2), the number-average molecular weight of described hard segment is in 200 to 2000 scopes, contain at least a being selected from by the vulcabond with symmetrical structure (a1), has the material in the lower molecular weight diamines (a2) of symmetrical structure and the group that low molecular weight diols (a3) is formed, it is 500～5000 high molecular weight diol (a4) that described soft chain segment (A2) contains number-average molecular weight, the content of hard segment is at 5 weight %～50 weight % in the described resin, the content of aromatic nucleus is smaller or equal to 35 weight % in the resin, and the content of aromatic nucleus and urea group satisfies following equation (i):
-0.1x+2.5≤y≤-0.1x+6???????????????(i)
Wherein, x represents the content (weight %) of aromatic nucleus in the resin (A), and y is the content (weight %) of urea group in the resin (A).
Molding among the present invention can further contain softening agent (B), inner pattern releasing agent applicable (C) and additive (D) with material.
In addition, the present invention also comprises a kind of moulded product by this molding is made with the material hot briquetting; A kind of slush molding shell of using by the automotive interior that this molding is made with the material hot briquetting; A kind of automotive interior material that comprises molding outer casing.
In addition, the present invention also comprises a kind of method of producing automotive interior instrument panel shell, described shell integrally has an air bag door part, described door part so preparation makes its tear line of tearing mouth can not be exposed on the design surface, this method comprises the step of tear line that molding is formed for tearing the door part of air bag with the step of material hot briquetting, at the molding that obtains by above-mentioned steps on material, and this tear line can not be exposed on the design surface.
Description of drawings
Fig. 1 is the TMA figure of employed urethane resin powder (F1) among the embodiment 1.
Fig. 2 is the TMA figure of the urethane resin powder (F8) of use in the comparative example 3.
Embodiment
For TPU(Thermoplastic polyurethanes) of the present invention (A), and Sti (measuring condition: temperature rise rate is 5 ℃/minute, loading capacity 5g, probe diameter is 0.5mm) in 135～200 ℃ of scopes, be preferably 145～180 ℃, more preferably 150～170 ℃.When Sti is lower than 135 ℃, the thermotolerance of shell will reduce; If Sti is higher than 200 ℃, the heat fusing characteristic is with variation under molding temperature.
In addition, the Δ ST that measures by the thermomechanical analysis osmose process is preferably 2～27 ℃, more preferably 3～25 ℃ in 0～30 ℃ of scope.When Δ ST surpasses 30 ℃, can not obtain melting characteristic and thermotolerance simultaneously.Resin with little Δ ST like this has sudden change fused characteristic.
Thermomechanical analysis osmose process method mentioned above can be referring to pretty " the thermoanalytical basis of material science " of writing of neat rattan peace [by upright altogether publication of nineteen ninety], the 350th page; Or referring to analyze " new thermoanalytical basis and application " [publishing] that association (Japan Society of Calorimetry and ThermalAnalysis) writes by Japanese thermal measurement and heat by Realize Corp., the 68th page, or open flat 10-259369 referring to the spy.
TPU(Thermoplastic polyurethanes) of the present invention (A) optimization polyurethane resin, for example, the urethane resin that contains hard segment (A1) and soft chain segment (A2), the number-average molecular weight of described hard segment (hereinafter being abbreviated as Mn) is in 200 to 2000 scopes, comprise at least a being selected from by the vulcabond with symmetrical structure (a1), has the material in the lower molecular weight diamines (a2) of symmetrical structure and the group that low molecular weight diols (a3) is formed, it is 500～5000 high molecular weight diol (a4) that described soft chain segment (A2) contains number-average molecular weight, the content of hard segment is at 5 weight %～50 weight % in the described resin, the content of aromatic nucleus is smaller or equal to 35 weight % in the resin, and the content of aromatic nucleus and urea group satisfies following equation (i):
-0.1x+2.5≤y≤-0.1x+6?????????????(i)
Wherein, x represents the content (weight %) of aromatic nucleus in the urethane resin, and y is the content (weight %) of urea group in the urethane resin.
In description of the invention, term " has symmetrical structure " and refers to the symmetrical structure that has linearity in the plane chemical structural formula of compound.
1. the vulcabond (a1) that has symmetrical structure
The example of vulcabond (a1) can comprise and has 2～18 carbon atoms (in the carbon atom in the NCO group is not included in, aliphatic diisocyanate down together), for example 1,2-ethylidene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter being abbreviated as HDI), 1,8-eight methylene diisocyanates, 1,12-ten dimethylene diisocyanates, etc.; Alicyclic diisocyanate with 4～15 carbon atoms, for example 4,4 '-dicyclohexyl methane diisocyanate (hereinafter being abbreviated as hydrogenation MDI), hexanaphthene-1, the 4-vulcabond, etc.; Aromatic base aliphatic diisocyanate with 8～15 carbon atoms, p-Xylol vulcabond for example, α, α, α ', α '-tetramethyl-eylylene diisocyanate, etc.; Aromatic diisocyanate with 6～18 carbon atoms, for example 4,4 '-diphenylmethanediisocyanate, etc.; Carbonates vulcabond with 3～17 carbon atoms, for example two (2-isocyanic acid ethyl) carbonic ethers, etc.; And (modified compound with symmetrical structure contains urethane group, carbodiimide group, urea group, urea diketone group and oxazolidone group to have the modified compound of vulcabond symmetrical structure; Deng); And the mixture that contains two or more above-claimed cpd.
Preferred compound comprises ethylene vulcabond, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-ten dimethylene diisocyanates, two (2-isocyanic acid ethyl) carbonic ether, 4,4 '-dicyclohexyl methane diisocyanate, hexanaphthene-1,4-vulcabond, p-Xylol vulcabond, α, α, α ', α '-tetramethylxylene diisocyanate, 4,4 '-diphenylmethanediisocyanate.Especially preferred compound comprises hydrogenation MDI and HDI, more preferably HDI.
The vulcabond of unsymmetric structure (a1 ') (for example, isophorone diisocyanate, trimethylammonium-1,6 ,-hexylidene diisocyanate etc.) also can use with above-described vulcabond (a1).For the usage quantity of the vulcabond of unsymmetric structure, consider melting behaviour, the mol ratio of (a1 ')/(a1) is preferably smaller or equal to 0.25.
2. the lower molecular weight diamines (a2) (diamines (a2) hereinafter referred to as) that has symmetrical structure
The example of diamines (a2) comprises the straight-chain alkyl-sub-diamines with 2～18 carbon atoms, for example ethylene diamines, 1,4-tetramethylene-diamine, 1,6-hexamethylene-diamine (hereinafter being abbreviated as HDA), 1,8-eight methylene diamine, 1,12-ten dimethylene diamines etc.; Alicyclic diamine with 4～15 carbon atoms, for example 4,4 '-dicyclohexyl methyl hydride diamines (hereinafter being abbreviated as MDA), hexanaphthene-1,4-diamines etc.; Aromatic base aliphatie diamine with 8～15 carbon atoms, p-Xylol diamines for example, α, α, α ', α '-tetramethyl-xylylene amine etc.; Aromatic diamine with 6～18 carbon atoms, for example 4,4 '-diamines-ditan etc.; Carbonates diamines with 3～17 carbon atoms, for example two (2-aminoethyl) carbonic ethers etc.; Polyoxyethylene diamines (molecular weight is smaller or equal to 500) etc.; Polyoxy tetramethylene-diamine (molecular weight is smaller or equal to 500); And the mixture that comprises two or more above-claimed cpd.
Preferred compound comprises the straight-chain alkyl-sub-diamines with 2～18 carbon atoms, two (2-aminoethyl) carbonic ether, 4,4 '-the dicyclohexyl methyl hydride diamines, hexanaphthene-1,4-diamines, p-Xylol diamines, α, α, α ', α '-tetramethyl-xylylene amine, 4,4 '-diamines-ditan.Preferred compound comprises ethylene diamine and hydrogenation MDA and HDA, especially preferred HDA.
As the combination of above-mentioned vulcabond (a1) and above-mentioned diamines (a2), the residue (except the amino) of preferred diamines (a2) has identical structure with the residue (except the isocyanato) of vulcabond (a1).The for example combination of HDI and HDA; The combination of two (2-isocyanic acid ethyl) carbonic ether and two (2-aminoethyl) carbonic ethers; The combination of hydrogenation MDI and hydrogenation MDA; Hexanaphthene-1,4-vulcabond and hexanaphthene-1, the combination of 4-diamines; The combination of p-Xylol vulcabond and p-Xylol diamines; α, α, α ', α '-tetramethyl-eylylene diisocyanate and α, α, α ', the combination of α '-tetramethyl-xylylene amine; 4,4 '-diphenylmethanediisocyanate and 4,4 '-combination of diamines-ditan; Deng.
The diamines of unsymmetric structure (a2 ') (for example, isophorone diamine, trimethylammonium-hexamethylene diamines etc.) also can use with above-mentioned diamines (a2).For the usage quantity of diamines (a2 '), consider melting behaviour, (a2 ')/(a2) be preferably smaller or equal to 0.25 in molar ratio.
Above-mentioned diamines (a2) can use with the form of ketoimine.Ketoimine comprises, for example, and by the ketoimine product that diamines and ketone (acetone, methyl ethyl ketone (hereinafter being abbreviated as MEK), the methyl iso-butyl ketone (MIBK) etc.) reaction with 3～6 carbon atoms are obtained.
3. low-molecular-weight glycol (a3)
Low-molecular-weight glycol (a3) comprises, for example, Mn is less than 500 glycol.
The illustrative examples of above-mentioned low-molecular-weight glycol (a3) comprises having aliphatic diol [straight diol (ethylene glycol, Diethylene Glycol, 1, the ammediol, 1 of 2～18 carbon atoms, 4-butyleneglycol (hereinafter being abbreviated as BG), 1,5-pentanediol, 1,6-hexylene glycol etc.), glycol (propylene glycol, neopentyl glycol, 3-methyl isophthalic acid with side chain, 5 pentanediols (hereinafter being abbreviated as MPD), 2,2-diethyl-1, ammediol, 1,2-, 1,3-or 2,3-butyleneglycol etc.)]; Glycol (disclosed among for example special public clear 45-1474, as to comprise cycloaliphatic ring group glycol (1,4-two (methylol) hexanaphthene, Hydrogenated Bisphenol A etc.) with cyclic group of 3～18 carbon atoms with 3～30 carbon atoms; Glycol ((and to) benzene two methylene glycols that comprise aromatic group) with 6～15 carbon atoms; Be selected from oxyalkylene (AO) affixture (the addition mole number is 2～6) of at least a material of the group of forming by pyrocatechol, Resorcinol, Resorcinol, dihydroxyphenyl propane, bisphenol S, Bisphenol F and dihydroxy naphthalene; Two or more mixture of the AO affixture of above-mentioned glycol (the addition mole number is 1～6) and they.
The example of above-mentioned AO affixture comprises oxyethane (EO), propylene oxide (PO), 1,2-, 1,3-, 1,4-and 2, has 5～10 or more than two or more mixture (block or addition at random) of the alpha-oxidation alkene of 10 carbon atom, epoxy chloropropane and they at 3-butylene oxide ring, Styrene oxide 98min..
Preferred in the above-mentioned low molecular weight diols (a3), for example, Mn is lower than 500 the glycol with symmetrical structure (a3 '), for example following general formula (1), (2) and (3) expression glycol [hereinafter being expressed as glycol (a3 ' 1), glycol (a3 ' 2), glycol (a3 ' 3) respectively], the EO affixture of above-mentioned glycol (a3 ' 1) or tetrahydrofuran (THF) (hereinafter being abbreviated as THF) affixture (a3 ' 4) have the glycol (a3 ' 5) of side chain, etc.; And two or more mixture in them.Wherein more preferably glycol (a3 ' 1), glycol (a3 ' 2) and glycol (a3 ' 3).
HO(CH
2)
m-(Q
1)
p-(CH
2)
mOH???????????????????????????????(1)
H(OCH
2CH
2)
nO-Q
2-O(CH
2CH
2O)
nH??????????????????????????(2)
H(OCH
2CH
2CH
2CH
2)
kO-Q
2-O(CH
2CH
2CH
2CH
2O)
kH??????????????(3)
In general formula (1), Q
1Be methylene radical, 1,4-cyclohexylidene or 1,4-phenylene, p are 0 or 1, m is that 0 or 1～6 integer is (if p is 0 or Q
1Be 1, the 4-phenylene, m is 1～6 so), in general formula (2) and general formula (3), Q
2Be the residue or 1 of bisphenols, 4-phenylene, n are integers 1～3, and in general formula (3), k is 1 or 2, works as Q
2When being the residue of bisphenols, k is 1.
Bisphenols comprises the represented group of following general formula (4).
In formula (4), G represents Direct Bonding, have the alkylene of 1～6 carbon atom, have alkylidene group, ring alkylidene group, arylmethylene alkyl, O, SO, the SO of 2～6 carbon atoms
2, CO, S, CF
2, C (CF
3)
2Or NH.
Glycol mentioned above (a3 ' 1) comprises for example, having the straight chain alkylene glycol such as the ethylene glycol, 1 of 2～18 carbon atoms, 4-butyleneglycol (hereinafter being abbreviated as BG), 1,6-hexylene glycol (hereinafter being abbreviated as HG), 1,8-ethohexadiol and 1,12-dodecyl glycol; Cycloaliphatic ring glycol with 4-15 carbon atom is as 1, two (methylol) hexanaphthenes and 1 of 4-, 4-cyclohexane diol; Have the aromatic base aliphatic diol of 8～15 carbon atoms such as terephthalyl alcohol etc.
Glycol mentioned above (a3 ' 2) comprises, for example, the EO of Resorcinol (2～6mol) affixtures, the EO of dihydroxyphenyl propane (2～6mol) affixtures, the EO of Bisphenol F (2～6mol) affixtures, the EO of bisphenol S (2～6mol) affixtures, etc.
Glycol mentioned above (a3 ' 3) comprises, for example, the THF of Resorcinol (THF of 2～4mol) affixtures, dihydroxyphenyl propane (THF of 2～4mol) affixtures, Bisphenol F (THF of 2～4mol) affixtures, bisphenol S (2～4mol) affixtures, etc.
Affixture mentioned above (a3 ' 4) comprises, for example, and Diethylene Glycol, triethylene glycol, etc.
Glycol mentioned above (a3 ' 5) comprises, for example, and neopentyl glycol etc.
The preferred example of glycol with symmetrical structure (a3 ') mentioned above comprises ethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,4-two (methylol) hexanaphthene and 1, the 4-cyclohexane diol, especially preferred is 1,4-butyleneglycol, 1,6-hexylene glycol, 1, two (methylol) hexanaphthenes of 4-.
Diamines mentioned above (a2) and low-molecular-weight glycol (a3) also can use separately, but preferred diamines (a2) and glycol (a3) are united use.Their mol ratio (a2)/(a3)=0.5～10 is preferably 1～5.
Among the present invention, by the Mn that is selected from least a hard segment of forming (A1) in the group that vulcabond mentioned above (a1), diamines (a2) and low-molecular-weight glycol (a3) constituted preferably in 200～2000 scopes, more preferably 300～1000.Consider sudden change fused characteristic, Mn is preferably more than and equals 200, considers STi, and Mn is preferably smaller or equal to 2000.The Mn of hard segment (A1) can (ii) calculate by following equation.
[weight of the weight+glycol (a3) of the weight+diamines (a2) of vulcabond (a1)]/
[mole number of the mole number-glycol (a3) of the mole number-diamines (a2) of vulcabond (a1)] (ii)
In addition, the content [total amount of vulcabond (a1)+diamines (a2)+glycol (a3)] of hard segment in the above-mentioned resin (A), consider the thermotolerance of shell, be preferably greater than and equal 5 weight %, consider STi, be preferably smaller or equal to 50 weight %, more preferably in the scope of 8 weight %～40 weight %, especially preferred in the scope of 10 weight %～30 weight %.
4. high molecular weight diol (a4)
The Mn of high-molecular weight glycol (a4) is preferably 500～5000, and more preferably 700～3000, and the ratio of its weight-average molecular weight (hereinafter being abbreviated as Mw) and Mn is preferably 1.0～3.0, especially is preferably 1.0～2.0.Consider texture and STi, Mn is preferably greater than and equals 500, and, consider sudden change fused characteristic, preferably smaller or equal to 5000.The Mw of glycol (a4) and Mn are that solvent is measured with THF by gel permeation chromatography (hereinafter being abbreviated as GPC).
The specific examples of above-mentioned glycol (a4) comprises, polyether glycol, polyester glycol, silicone glycol, polybutadiene diol, acryloyl glycol, polymer diol (glycol that obtains by the vinyl monomer in the polymerization macromolecule amount glycol) and two or more mixture in them.Preferred examples comprises polyether glycol and polyester glycol.
Polyether glycol comprises, for example, by AO being added in the compound with two active hydrogen atoms (dibasic alcohol, dihydric phenol, unary primary amine etc.) and the compound that makes, and composition thereof etc.
Dibasic alcohol mentioned above comprises, for example, and alkylene glycol such as ethylene glycol, Diethylene Glycol, 1,2-propylene glycol, 1,3-and 1,4-butyleneglycol, 1, has the glycol (for example compound disclosed in the patent of special public clear 45-1474) of cyclic group etc. at 6-hexylene glycol, neopentyl glycol.Dihydric phenol comprises monocyclic polyphenol such as pyrogallol, Resorcinol, and Phloroglucinol; Bis-phenol such as dihydroxyphenyl propane, bisphenol S, Bisphenol F etc.
The preferred dibasic alcohol of compound with two active hydrogen atoms, especially 1, the 4-butyleneglycol.
The example of AO comprises the AO with 2～8 carbon atoms, the AO of replacement such as EO, PO, 1,2-, 1,3-and 2,3-oxybutylene, THF, Styrene oxide 98min., two or more this combination of compounds (block or random addition) etc.The composition of wherein preferred PO and EO and PO.
Polyester glycol comprises, for example, and 1. condensation polyester glycol, 2. polylactone glycol, 3. polycarbonate diol, and their two or more combination of compounds.
1. condensation polyester glycol mentioned above can make by following method, for example, by one or more glycol (low molecular weight diols and/or polyether glycol etc.) and a kind of dicarboxylic acid maybe can being formed derivative [low alkyl group (carbonatoms is 1～4) ester, acid anhydrides, halogenide (muriate etc.) etc.] polycondensation of its ester, or, a kind of glycol makes by being reacted with a kind of di-carboxylic acid acid anhydrides and AO.
Polylactone glycol mentioned above 2. can be by obtaining as the ring-opening polymerization that initiator carries out lactone with one or more above-mentioned glycol.
Polycarbonate diol mentioned above 3. can be by obtaining above-mentioned glycol and a kind of alkylene carbonate (ethylidene carbonic ether) reaction.
As above-mentioned polyester glycol 1., 2., 3. raw material glycol, low molecular weight diols can comprise, for example, aliphatics low molecular weight diols (ethylene glycol, Diethylene Glycol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol etc.); Have cyclic group low molecular weight diols [for example, disclosed glycol in the patent of special public clear 45-1474: 1, two (methylol) hexanaphthenes of 4-, or terephthalyl alcohol etc.]; The low mole of the oxyalkylene of bis-phenol affixture (molecular weight is lower than 500); Two or more combination etc. in them.Polyether glycol can comprise, for example, one or more polyether glycols mentioned above, preferred 1,4-butyleneglycol, 1,6-hexylene glycol.
As above-mentioned condensation polyester glycol 1. the dicarboxylic acid of raw material comprise, for example, aliphatic dicarboxylic acid (succsinic acid, hexanodioic acid, sebacic acid, pentanedioic acid, nonane diacid, maleic acid, FUMARIC ACID TECH GRADE etc.) with 2～10 carbon atoms, aromatic dicarboxylic acid (terephthalic acid, m-phthalic acid etc.) with 8～12 carbon atoms, two or more combination etc. in them.
Above-mentioned condensation polyester glycol 1. preferred examples comprises poly-hexanodioic acid fourth diester diol (PBA) and polyhexamethylene m-phthalic acid esterdiol (PHIP) and their combination etc.
As above-mentioned polylactone glycol 2. the lactone of raw material comprise, for example, gamma-butyrolactone, γ-Wu Neizhi, 6-caprolactone and two or more combination thereof etc.
The content x of aromatic ring is preferably smaller or equal to 35 weight % in the above-mentioned resin (A), and urea group content (weight %) y preferably satisfies following formula (i).In other words, from the angle of melting behaviour, y preferably is no more than-0.1x+6, and from stable on heating angle, y equals-0.1x+2.5 at least, and from cryogenic properties, x is preferably smaller or equal to 35 weight %.
-0.1x+2.5≤y≤-0.1x+6???????????????(i)
In addition, preferably satisfy following formula (i "), and x is 1～30 weight %.
-0.1x+2.5≤y≤-0.1x+5.5?????????????(i″)
Especially, preferably satisfy following formula (i ), and x is 1～30 weight %.
-0.1x+2.5≤y≤-0.1x+5???????????????(i)
From the angle of wear resistance, most preferably satisfying following formula (i ') and x is 5～25 weight %.
-0.1x+3≤y≤-0.1x+5?????????????????(i′)
In the specification sheets of the present invention, the content of aromatic ring part in " aromatic ring content " expression resin.In " urea group content " expression resin-content of NHCONH-group.
For the Mn of TPU(Thermoplastic polyurethanes) among the present invention (A), from the angle of mechanical strength of resin, be preferably greater than and equal 4000, from the angle of STi, preferably smaller or equal to 40000, more preferably 8000～25000.
Mn adopts N by the GPC method, and dinethylformamide (hereinafter being abbreviated as DMF) is measured as solvent.
Above-mentioned resin (A) can prepare by single stage method, described single stage method relates to the vulcabond (a1) with above-mentioned symmetrical structure and compound [above-mentioned diamines (a2) and/or above-mentioned glycol (a3) with active hydrogen atom, with above-mentioned high molecular weight diol (a4), in case of necessity polymerization stops thing (a5)] single step reaction; Or to form with NCO by the reaction that relates to glycol [above-mentioned high molecular weight diol (a4) and above-mentioned glycol (a3) in case of necessity] and the polymerization terminator that depends on the needs and excessive vulcabond (a1) be terminal urethane prepolymer (hereinafter being abbreviated as Up), Up reacted with the residual component that active hydrogen atom is arranged [diamines (a2) and/or glycol (a3) and polymerization terminator in case of necessity (a5)] to prepare then.The prepolymer method is preferred.
Above-mentioned resin (A) preferably obtains with powder type.The method that obtains resin (A) powder comprises that the block or globular resin (A) that 1. adopts grindings such as cooling off polishing, freeze grinding method to obtain with aforesaid method obtains the method for powdery resin (A); 2. do not having solvent to exist or having under the situation of solvent existence, Up is dispersed in the water that contains dispersion stabilizer with high speed agitator, and with the method for gained material and water and/or diamines (a2) and polymerization terminator (a5) reaction that depends on the needs, described Up is reacted by high molecular weight diol (a4) and the glycol (a3) that depends on the needs and/or polymerization terminator (a5) and excessive vulcabond (a1) and obtains; 3. do not having solvent to exist or having under the situation of solvent existence, will with as 2. described in the Up of method preparation be dispersed in the non-water-dispersion solvent (hexane, heptane etc.) that contains dispersion stabilizer the method that gained material and diamines (a2) and the polymerization terminator (a5) that depends on the needs etc. are reacted then.1. in 3., polymerization terminator (a5) can add in the production of prepolymer, also can add in the production of urethane resin in method.In these methods, 2. the preparation method is especially preferred method.
At aforesaid method 2. and 3., the mixture (M) of the above-mentioned polymerization terminator of deciding with the Up of 100 weight parts, above-mentioned diamines (a2) with on necessity (a5) is a benchmark, from the dispersion state of mixture (M) and the granularity of the toner that obtains, the amount of the stably dispersing agent solution of being formed by dispersion stabilizer and water or non-water-dispersion solvent, be preferably more than and equal 50 weight parts, more preferably 100～1000 weight parts.In addition, if desired, can reduce the viscosity of mixture (M) by heating (for example 40～100 ℃), be that organic solvent inert such as esters solvent, ketones solvent, chlorinated solvents or aromatic solvents also can add with respect to vulcabond.The rotating speed of high speed dispersion device preferably is at least 1000rpm, more preferably 3000～10000rpm.
In the case, the back adds in the water although above-mentioned diamines (a2) and the polymerization terminator (a5) that depends on the needs can be distributed at Up, perhaps adds before Up is about to disperse, and considers that the order reaction carries out more equably, preferred after a kind of mode.
Above-mentioned polymerization terminator (a5) comprises, for example, have 1～12 carbon atom monohydroxy-alcohol (the oxyalkylene affixture of methyl alcohol, ethanol, propyl carbinol, n-Octanol, 2-Ethylhexyl Alcohol, cellosolvo, phenol etc.), have the monoamine [diethylamide, dibutylamine (hereinafter being abbreviated as DBA), diethanolamine etc.] of 1～12 carbon atom etc.Wherein, preferred monohydroxy-alcohol, especially preferred n-Octanol and 2-Ethylhexyl Alcohol.
In urethane (urethanization) reaction, optionally can use known catalyzer.The illustrative examples of catalyzer comprises that [tin-based catalyst is as dibutyl tin laurate, two lauric acid dioctyl tins, stannous octoate etc. for organometallic compound; Lead base catalyzer such as lead octoate 36 etc.]; [(San-Apro Lt. produces amine, DBU) etc. for triethylamine, triethylenediamine, diaza-bicyclo undecylene; And two or more combination etc.Catalyst consumption is had no particular limits, and still the weight part in above-mentioned resin (A) is 100, is preferably 0.001～0.05 weight part.
In the urethane reaction, optionally can use known solvent (THF, DMF, toluene, MEK etc.).
The second-order transition temperature of above-mentioned resin (A) (hereinafter being abbreviated as Tg) is preferably-60 ℃～-35 ℃, more preferably-45 ℃～-35 ℃, has the material of the instrument panel shell of air bag door part on the whole as being used for molding, described door part is made like this, and the tear line that is used for tearing is not exposed on the design surface.Tg can use differential scanning calorimeter (hereinafter being abbreviated as DSC) to measure.
The Tg of resin (A) surpasses-35 ℃, when air bag expands, occurs in part beyond tearing mouthful easily and ftractures and tear, especially under low temperature or analogue.In addition, for urethane resin, the lower limit of Tg should be-60 ℃.
The material that the present invention is used for molding can only contain above-mentioned resin (A), also can further contain softening agent (B).In addition, optionally, resin (A) or resin (A) and softening agent (B) can contain a kind of in inner pattern releasing agent applicable (C) and the additive (D) at least, and described inner pattern releasing agent applicable (C) is used for the moulding material of slush molding polyurethane outer.
Above-mentioned softening agent (B) comprises, for example, and phosphoric acid ester; The aromatic base monocarboxylic acid diester of poly-(polymerization degree is 3～10) alkylene (carbonatoms is 2～3) glycol; Phthalic ester [dibutyl phthalate, dioctyl phthalate (DOP), phthalic acid dibutyl benzyl ester, Di Iso Decyl Phthalate etc.]; Aliphatic dicarboxylic acid ester [two-2-ethylhexyl adipic acid ester, 2-ethylhexyl sebate etc.]; Trimellitate [three-2-ethylhexyl trimellitate, trioctylphosphine trimellitate etc.]; Aliphatic ester [butyl oleate etc.]; The mixture of two or more above-mentioned substance etc.
Angle from humidity resistance, above-mentioned softening agent (B) preferably phosphoric acid ester, the phosphoric acid ester (B1) of especially following general formula (5) expression, from low-temperature performance, especially at low temperatures the character angle of tearing of air bag door is set out, preferred below poly-(polymerization degree is 3～10) alkylene carbonatoms of general formula (7) expression be 2～3) glycol (and aromatic base monocarboxylic acid diester (B2).
In the formula (5), R is for having the monovalence alkyl of 1～10 carbon atom independently, and it can have halogen to replace, a plurality of R can be identical also can be different, R ' is the divalent organic group with 2～15 carbon atoms, it can have halogen to replace, q is 1～6 integer.
The example of R comprises having the aliphatic alkyl (methyl, ethyl, sec.-propyl, normal-butyl, the tertiary butyl, hexyl etc.) of 1～10 carbon atom; Selectivity is had the aromatic hydrocarbyl of the alkyl replacement of 1～4 carbon atom, (phenyl, xylyl, tolyl, ethylphenyl, butyl phenyl etc.); The above-mentioned group of halogen replacement etc. is arranged.Preferred R is a phenyl, alkyl phenyl, or the phenyl that has halogen to replace.
The example of R ' comprises having the divalence aliphatic alkyl (ethylidene, propylidene, inferior normal-butyl, the inferior tertiary butyl, hexylidene etc.) of 2～15 carbon atoms; Selectivity with 6～15 carbon atoms contain the divalence aromatic hydrocarbyl of sulphur atom or Sauerstoffatom [phenylene, diphenylene ,-Ph-CH
2-Ph-,-Ph-C (CH
3)
2-Ph-,-Ph-SO-Ph-(Ph represents phenylene), the residue in the bis-phenol (dihydroxyphenyl propane, Bisphenol F, bisphenol S etc.) beyond the hydroxyl-removal etc.]; The above-mentioned group of halogen replacement etc. is arranged.
Preferably include the divalence aromatic hydrocarbyl with 6-15 carbon atom, described divalence aromatic hydrocarbyl can contain sulphur atom or Sauerstoffatom.
In each example of above-mentioned phosphoric acid ester (B1), especially preferably by the softening agent of general formula (5) representative, wherein R is phenyl, alkyl phenyl or halogenophenyl, and R ' is represented by following general formula (6):
-Ph′-(A-Ph′)
p-??????????????(6)
In general formula (6), Ph ' represents 1, and 4-phenylene, p are 0 or 1, and A is Direct Bonding, methylene radical, isopropylidene or SO.
Above-mentioned aromatic series monoprotic acid diester (B2) comprises the compound by following formula (7) expression:
R wherein
1And R
2Be identical or different aromatic series monocarboxylic acid residue, T is the alkylene with 2～4 carbon atoms, and n is 1～10 integer.
R
1And R
2Comprise the alkyl that can be had 1～10 carbon atom or halogen (Cl, Br etc.) aromatic hydrocarbyl (phenyl, tolyl, xylyl substitution in ring (substitution value is 1～3), the 4-butyl phenyl, 2,4-dibutyl phenyl, 2-methyl-4-chloro-phenyl-, nonyl phenyl etc.).
In addition, the example of T comprises straight or branched alkylene (ethylidene, 1, the 2-and 1 with 2～4 carbon atoms, the 3-propylidene, 1,2-, 2,3-, 1,3-and tetramethylene etc.), and the halo group of these groups (1-chloromethyl ethylidene, 1-brooethyl ethylidene etc.).
The specific examples of aromatic series monocarboxylic acid diester (B2) comprises polyoxyethylene glycol (polymerization degree is 3～10) dibenzoate, polypropylene glycol (polymerization degree is 3～10) dibenzoate etc.
Above-mentioned phosphoric acid ester (B1) and aromatic series monocarboxylic acid diester (B2) can use or unite use separately separately or unite use with one or more other above-mentioned softening agent.When uniting use, especially with regard to phosphoric acid ester (B1), consider from anti-hygroscopic property aspect, with regard to aromatic series monocarboxylic acid diester (B2), especially consider from the aspect of performance of tearing in low temperature space-time air bag doors, the content of phosphoric acid ester (B1) or aromatic series monocarboxylic acid diester (B2) is preferably greater than and equals 50 weight % in the above-mentioned softening agent (B), especially is preferably greater than to equal 70 weight %.
In slush molding material of the present invention, based on the resin (A) of 100 weight parts, the blending ratio of softening agent (B) is preferably smaller or equal to 80 weight parts, more preferably 2～70 weight parts, more preferably 5～50 weight parts.For the blending ratio of softening agent, consider the melt viscosity in the molding, overtime more preferably greater than equaling 2 weight parts, consider to ooze out, preferably smaller or equal to 80 weight parts.
Inner pattern releasing agent applicable (C) is preferably a kind of being selected from by the phosphoric acid ester (salt) of the fluorine modification of general formula (11) expression (f) and contain compound in the group that the siloxanes of the modification of following polar group (c) forms.
The siloxanes that contains the modification of following polar group (c) selects the carboxy-modified organopolysiloxane (c1) of free style (8) expression at least, the epoxide modified organopolysiloxane (c2) of formula (9) expression, and a kind of in the group formed of the organopolysiloxane (c3) of the ether modification of formula (10) expression.
This class material can improve in traditional inner pattern releasing agent applicable, in surface and the polyurethane foam, and the difficult problem of consistency between enough demoulding effects and the adhesion characteristics.The phosphoric acid ester of fluorine modification (salt) is represented phosphoric acid ester or its salt of fluorine modification.
(R
f-D-O)
rP(＝O)(OH
3)
t???????????????????????????(11)
In (10), Q is usefulness-R in formula (8)
2The carboxyl that COOH represents; X is for using
Or
The epoxy group(ing) of expression; Z is usefulness-C
3H
6O (C
2H
4O)
p-(C
3H
6O)
qR
3The polyether group of expression; R
1Be alkyl with 1～4 carbon atom, R
2Be alkylene with 1～4 carbon atom, R
3Be H, have the alkyl or the ethanoyl of 1～4 carbon atom, Me is a methyl; A, b and c are 0 or 1 independently of one another, and if meet a=1 and b=1 then the restricted condition of c=0; M and n meet (m+n) between 10～200 and the numeral of the condition of n/ (m+n) between 0～0.5; P and q meet (p+q) between 3～100 and the numeral of the condition of p/ (p+q) between 0～0.6.
In addition, in the formula (11), R
fIt is perfluoroalkyl with 4～20 carbon atoms; D is by-CH
2CH (E) C
sH
2s-or-SO
2N (R
4) C
tH
2tThe divalent organic group of-expression, wherein E is H, CH
3, C
2H
5, Cl or OR
5(R
5Be H, CH
3, C
2H
5, COCH
3, COC
2H
5, or CH
2COOH or its salt), s is 0～4 integer, R
4Be the alkyl with 1～4 carbon atom, t is 1～4 integer; R is integer 2 or 3.
Consider release property, arrive in (11) R in formula (8)
1The alkyl that preferably has 1～4 carbon atom (more preferably 1～3 carbon atom).Consider release property, R
2The alkylene that preferably has 1～4 carbon atom (more preferably 1～3 carbon atom).
Consider release property, R
3Be preferably H or have the alkyl or the ethanoyl of 1～4 carbon atom (more preferably 1～3 carbon atom).
M and n are the numeral that satisfies following condition: consider release property, preferably meeting (m+n) is more than or equal to 10, consider shell in the polyurethane foam with shell as described below and the adhesion property between the foam, preferably (m+n) is smaller or equal to 200 (more preferably 25～100), and consider release property, n/ (m+n) is 0～0.5 (more preferably 0.1～0.45).
P and q are the numeral that satisfies following condition: consider the adhesion characteristics between shell and foam, (p+q) be preferably greater than and equal 2, consider release property, (p+q) smaller or equal to 100 (more preferably 3～60), and p/ (p+q) is preferably greater than and equals 0.01, consider the anti-hygroscopic property of shell, p/ (p+q) is smaller or equal to 0.6 (more preferably 0.05～0.3).
Yet a, b and c be 0 or 1[do not comprise the situation [compound is not the material by organic group (carboxyl, epoxy group(ing) or ether) modification] of a=1, b=1 and c=0], the siloxanes of modification comprises following kind.
[1] side chain type: wherein a=1, b=0, c=1; Introduce an organic group in the organopolysiloxane side chain.
[2] two tip type: wherein a=0, b=1, c=0; Two ends of organopolysiloxane are all introduced an organic group.
[3] single tip type: wherein a=1, b=1 and c=0 or a=0, b=1 and c=1; Introduce an organic group in the end of organopolysiloxane.
[4] the two tip type of side chain: wherein a=0, b=0, c=0; Two ends and the side chain of organopolysiloxane are introduced an organic group respectively.
[5] side chain list tip type: wherein a=1, b=0 and c=0 or a=0, b=0 and c=1; The end and the side chain of organopolysiloxane are introduced an organic group respectively.
[6] mixed type: two or more is selected from the mixed type of above-mentioned [1] to [5].
The carboxyl acid modified organopolysiloxane (c1) of above-mentioned general formula (8) expression is considered release property, is preferably side chain type (c11), two tip type (c12), mixed type (c16), more preferably mixed type (c16).
The preferred example of side chain type (c11) comprises having 3,000～4, the normal material of 000 carboxylic acid, (m+n) in 20～200 scopes, n/ (m+n) is in 0.01～0.1 scope, for example, commodity are called X-22-3701E (SHIN-ETSU HANTOTAI's chemical industry (strain) production), commodity are called SF8418 (Dow CorningToray Silicone Co., Ltd produces) etc., more preferably X-22-3701E.
The preference of two tip type (c12) specifically comprises having 800～1, the normal material of 500 carboxylic acid, and (m+n) in 10～100 scopes, n/ (m+n) is 0, for example, commodity are called X-22-162A (production) etc.
The preference of mixed type (c16) comprises having 1,000～1, the normal material of 500 carboxylic acid, and (m+n) in 10～100 scopes, n/ (m+n) is in 0～10 scope, and for example, commodity are called X-22-3710 (SHIN-ETSU HANTOTAI's chemical industry (strain) production) etc.
In epoxide modified organopolysiloxane (c2) by above-mentioned formula (9) expression, consider from release property, preferably include side chain type (c21).
The preferred example of side chain type (c21) specifically comprises having 2,500～4, the material of 500 epoxy equivalent (weight), (m+n) in 10～200 scope, n/ (m+n) is in 0.1～0.5 scope, for example, commodity are called KF-1001, KF101, KF-102 (producing by SHIN-ETSU HANTOTAI's chemical industry (strain)), commodity SF8411 by name and SF8413 (by Dow Corning Toray Silicone Co., Ltd produces) etc., more preferably KF-1001 and KF-102.
In the organopolysiloxane (c3) of the ether modification of representing by formula (10), consider from release property, preferably include side chain type (c31).
The example of preferred side chain type (c31) comprises (m+n) in 10～50 scope, the material of n/ (m+n) in 0.05～0.5 scope, for example, commodity FZ-2222 by name and FZ-2164 (by Nippon Unicar Co., Ltd produces) etc.
The phosphoric acid ester (salt) of above-mentioned general formula (11) expression fluorine modification (f), the phosphoric acid ester of described fluorine modification (salt) comprises following example.
(a) mixture of i＞=3 is with [(CF
3) CF (CF
2CF
2)
iCH
2CH (OH) CH
2O]
rPO (OH)
3-rExpression
(b)[CaF
17SO
2N(C
2H
5)]CH
2CH
2O]
rPO(OH)
3-r
(c)[C
7F
15CH
2CH
2O]
rPO(OH)
3-r
(d) mixture of i＞=3 is with [(CF
3)
2CF (CF
2CF
2)
iCH
2CH
2CH
2O)
nPO (OH)
3-rExpression
(e)[(CF
3)
2CF(CF
2CF
2)
3CH
2CH(Cl)CH
2O]
rPO(OH)
3-r
(f)[(CF
3)
2CF(CF
2CF
2)
3CH
2CH(CH
3)O]
rPO(OH)
3-r
(g)[(CF
3)
2CF(CF
2CF
2)
3CH
2CH(OCH
2COOH)CH
2O]
rPO(OH)
3-r
In addition, the explanation example of the phosphate ester salt of fluorine modification comprises basic metal (sodium, potassium etc.) salt, ammonium salt, amine salt etc.
The phosphoric acid ester of fluorine modification (salt), from the angle of release property, preferred R wherein
fFor having the perfluoroalkyl of 7～20 carbon atoms, D contains alkyl or polarity atomic radical, as OH, and-OCH
2COOH-,-SO
2N (R)-, respectively do for oneself 1～3 integer of s, t, and the salt of such phosphoric acid ester, for example trade(brand)name Sumimold FA[is by living ore deposit lubricant (strain) production].
Inner pattern releasing agent applicable (C), from release property, preferably include carboxyl acid modified organopolysiloxane (c1) (in this section, be designated as (c1)) or the organopolysiloxane (c3) of ether modification (in this section, be designated as (c3)), or at least a being selected from by the material in (c1), epoxide modified organopolysiloxane (c2) and the group that (c3) constitutes and phosphoric acid ester (salt) composition (f) of fluorine modification, more preferably comprise (c1) and composition (c3), especially preferred is the composition that comprises mixed type (c1) and side chain type (c3).
In the weight of resin (A), the usage quantity of inner pattern releasing agent applicable (C) is from release property with to the adhesion property of polyurethane foam, preferred 0.01 weight %～5 weight %, more preferably 0.1 weight %～2 weight %.
The method that adds inner pattern releasing agent applicable (C) in resin (A) can be to mix the powder of inner pattern releasing agent applicable (C) and resin (A), perhaps adds reagent when forming resin (A) in advance in polyether polyols with reduced unsaturation.From release property, preferably with the method for the powder mixes of inner pattern releasing agent applicable (C) and resin (A).
The example of additive (D) comprises pigment, stablizer and other additives.
Pigment is not particularly limited, can comprises, for example, the pigment dyestuff of known use and/or mineral dye.Weight part in above-mentioned resin (A) is 100, preferred 0～5 weight part of the mixed volume of pigment.
Pigment dyestuff comprises, for example, and insoluble azo pigment, soluble azo pigment, copper phthalocyanine class pigment, quinacridone class pigment etc.; Mineral dye comprises, for example, and chromic salt, Ferrocyanide salt, metal oxide, selenium sulfide compound, metal-salt (vitriol, silicate, carbonate, phosphoric acid salt etc.), metal-powder, carbon black etc.
Stablizer is not particularly limited, can uses for example known antioxidant and/or UV light absorber.Weight part in above-mentioned resin (A) is 100, preferred 0～5 weight part of the mixed volume of stablizer.
Antioxidant comprises for example phenol antioxidant [2,6-two-tertiary butyl-p-cresol, butyl hydroxyanisole etc.]; The bisphenols antioxidant [2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) etc.]; Phosphorus antioxidant [triphenyl phosphorous acid ester, phenylbenzene isodecyl phosphorous acid ester etc.] etc.
UV light absorber comprises for example benzophenone absorption agent [2,4-dihydroxyl benzoyl benzene, 2-hydroxyl-4-methoxyl group benzoyl benzene etc.]; The benzotriazole category absorption agent [2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole etc.]; Salicylate [salol etc.]; Hindered amines absorption agent [two (2,2,6,6-tetramethyl--4-piperidines) sebate etc.] etc.
Other additives comprise, for example, and anti-hard caking agent, external release agent, fire retardant etc.
Anti-hard caking agent is not particularly limited, can uses known inorganic anti-hard caking agent, organic anti-hard caking agent.Inorganic anti-hard caking agent comprises, for example, and silicon-dioxide, talcum, titanium oxide, lime carbonate etc.; Organic anti-hard caking agent comprises, for example, have the thermosetting resin (thermosetting polyurethane resin of particle diameter smaller or equal to 10 μ m, guanamine resin, Resins, epoxy etc.), have the thermoplastic resin (TPU(Thermoplastic polyurethanes), poly-(methyl) acrylic resin etc.) of particle diameter, maleimide phthalate powder etc. smaller or equal to 10 μ m.
Weight part in above-mentioned resin (A) is 100, and the mixed volume of anti-hard caking agent is preferably 0～2 weight part.
External release agent is not particularly limited, can use known external release agent, for example fluorine-containing releasing agent (fluoroalkyl phosphoric acid ester etc.), silicon class external release agent (dimethyl polysiloxane, amino modified dimethyl polysiloxane, carboxy-modified dimethyl polysiloxane etc.), fatty acid ester external release agent (alkanoic acid (C11～24) alkane alkene (C6～24) ester etc.), phosphoric acid ester external release agent (Tributyl phosphate ester) etc.Weight part in above-mentioned resin (A) is 100, and the mixed volume of external release agent is 0～2 weight part.
Fire retardant is not particularly limited, can uses known fire retardant, for example, phosphoric acid ester, hydrogen halide based flame retardant etc.
The phosphoric acid ester fire retardant comprises, for example, and Tritolyl Phosphate (TCP), three (β-chloroethyl) phosphoric acid ester, three (two chloropropyls) phosphoric acid ester, three (dibromopropyl) phosphoric acid ester, bromo phosphoric acid ester etc.The hydrogen halide based flame retardant comprises, for example, and chloro paraffin and ethylene tetrabromide.The halogenated hydrocarbon fire retardant preferably uses with weisspiessglanz, zinc borate etc.Weight part in above-mentioned resin (A) is 100, and the mixed volume of fire retardant is preferably 0～20 weight part.
Weight part in above-mentioned resin (A) is 100, and the total amount of sneaking into of additive (D) is preferably 0～34 weight part, more preferably 0.05～20 weight part.
The method of production slush molding raw material of the present invention has no particular limits, but when containing above-mentioned softening agent (B) and above-mentioned additive (D), for example, can adopt following method.
1. the powder of above-mentioned resin (A), blocky softening agent (B) and additive (D) are concentrated the blended method with agitator.
2. described softening agent (B) and additive (D) are pre-mixed, then with the method for the powder mixes of described resin (A).
3. in any stage of producing resin (A) powder process, add the method for part or all of softening agent (B) and additive (D).
In these methods, consider that from the angle of simplifying production stage preferred method 2..
When using above-mentioned inner pattern releasing agent applicable (C), can be in advance with the powder mixes of itself and resin (A), perhaps can be with softening agent (B) and additive (D) powder mixes with resin (A).
Among the present invention, the equipment that is used to produce the slush molding raw material is not done special restriction, can use known powder mixes device.
The powder mixes device comprises, for example, and high speed shear mixing device [Henschel mixer (registered trademark) etc.], low speed mixing device [Nauta mixer (registered trademark), planetary mixer etc.] etc.
Consider the flowability of powder and the performance that powder enters the tiny position of slush molding model, the present invention is used for the equal particle diameter of body of slush molding material, be preferably greater than and equal 100 μ m, especially be preferably greater than and equal 130 μ m, consider the occurrence rate of pin hole on the molded plastic shell, preferably smaller or equal to 500 μ m, especially preferably smaller or equal to 200 μ m.
In addition, from because the performance that powder enters the tiny position of model when the flowability of the operating environment that causes of dust and powder and slush molding, particle diameter is smaller or equal to the proportion of particles of 75 μ m, preferably smaller or equal to 20 weight %, especially preferably smaller or equal to 15 weight %.
In the specification sheets of the present invention, the equal particle diameter of body be meant adopt laser scattering method can be with the undersized particle size values of 50% particle.Surveying instrument comprises, for example, and Microtrack HRA particle-size analyzer 9320-X100 (by Nikkiso Co., Ltd. produces).
For the employed moulding material that is used for moulding in the slush molding method of the present invention, for example, be suitable for adopting a kind of method, relate to shake to rotate the chest of molding of the present invention with dusty material is housed, and be heated to 200～280 ℃, make powder melt-flow in mold, cooling curing is made shell then.
The example of slush molding method program of the present invention is the row content as follows:
At first, in case of necessity, can under smaller or equal to 60 ℃ temperature, adopt the method for air-atomizing or brushing with known common external release agent commonly used (fluorine cpd type releasing agent, silicon compound type releasing agent etc.) be applied to mold, mold heated (200～300 ℃) by methods such as hot sand heating, oil heating.Molding of the present invention will be housed then be close to mold with the chest of dusty material, rotation is to import molding in the cavity with material.Rotation (powder adherence) is after 5～45 seconds, and excessive molding is removed with material, keeps then 60～300 seconds, and preferred 70～120 seconds so that the moulding material thawing.Afterwards, with cooling molds such as water coolings, remove mold then and obtain the hollow mould plastomer.
With the thickness preferred 0.5～1.5mm of molding of the present invention with the molded plastic shell of forming materials.This shell is suitable as the material inside of automobile, for example the shell of instrument panel, architrave etc.
The material that the present invention is used for molding instrument panel shell is suitable for preparing the automobile instrument panel enclosure that integrally has an air bag door part, and its tear line that is used to tear can not be exposed to design surface.The instrument panel shell made from shell formed material of the present invention integrally has an air bag door part, and the tear line that wherein is used to tear can not appear at the design surface of air bag door part.
The example of instrument panel shell comprises that a kind of spy of being disclosed in opens in the patent application of flat 10-86703.Replace wherein disclosed polyvinyl chloride, shell can be made with similar method molding with shell molding material of the present invention.
The preparation method of instrument panel shell of the present invention can suitably adopt and comprise the step of previous materials being carried out hot-moulded, forms the step of tearing with tear line on the moulding material that previous step obtains, and wherein tear line can not be exposed on the design surface.
Above-mentioned hot-moulded step is not particularly limited, can uses known method.For example, it also can be the conventional slush molding method that adopts in the instrument panel shell of making.
Step to above-mentioned formation tear line is not particularly limited yet, and can use known method.For example, adopt laser processing, blade press process etc. to form the step of tear line at the dashboard back side.
This tear line sheating material when airbag inflation can be torn along tear line.
Embodiment
Below, provide preparation embodiment and embodiment explaining the present invention in more detail, but the present invention is not limited in these embodiment.
In the raw material among the following embodiment, polyvalent alcohol I is that Mn is 1000 PBA, and polyvalent alcohol II is that Mn is 900 PHIP, and polyvalent alcohol III is that Mn is 2000 polyethylene adipate.Stablizer I is Irganox 1010, available from Ciba company limited; Titanium dioxide is TipaqueR-820, available from the former industry of stone (strain); Dispersion agent I is Sansparl PS-8, changes into industry (strain) available from Sanyo; Ketoimine I is the MEK ketoimine of HAD, and ketoimine II is the MEK ketoimine of hydrogenation MDA; Ketoimine III is the MEK ketoimine of isophorone diamines; Decollator I is Ultradisperser (a super decollator), available from Yamato Scientific Co., Ltd.; Softening agent I is CR741, available from big eight chemistry (strain).[by the phosphoric acid ester of general formula (5) expression, wherein R is a phenyl, and q is 1, and R ' is-ph-isopropylidene-ph-]; Softening agent II is Sansoft EB300, available from foreignizing industry (strain); Inner pattern releasing agent applicable is X22-3710, available from SHIN-ETSU HANTOTAI's chemical industry (strain).[carboxy-modified organopolysiloxane], anti-hard caking agent I are maleimide phthalate powder (the equal particle diameter of body is 3 μ m, and fusing point is 280 ℃).
Preparation example 1-8
According to scheme in the following table 1 (weight part is represented with part in table) preparation Up solution (Up1-Up8).
In the reaction vessel of being furnished with thermometer, agitator and nitrogen flushing pipe, the polyvalent alcohol of packing into, low molecular weight diols and 1-octanol with nitrogen exchange air wherein, with gained mixture heating up to 110 ℃, stir until thawing.To wherein adding vulcabond, mixture 85 ℃ of heating 6 hours, is formed a kind of Up with NCO end then.Then, Up is cooled to 60 ℃, adds THF afterwards, stablizer and titanium dioxide (in Up7, be cooled to 60 ℃ then add DBA) are uniformly mixed to form Up solution.The NCO content of these Up solution (weight % represents with % in table) is as shown in table 1.
Table 1
| Preparation example | ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 | ??8 |
| Polyvalent alcohol I (part) | ??575 | ??950 | ??800 | ??100 | ??946 | ??200 | ??- | ??570 |
| Polyvalent alcohol II (part) | ??383 | ??- | ??- | ??810 | ??- | ??720 | ??- | ??387 |
| Polyvalent alcohol III (part) | ??- | ??- | ??- | ??- | ??- | ??- | ??1271 | ??- |
| 1-octanol (part) | ??16.8 | ??17.2 | ??21 | ??16.6 | ??16.7 | ??18.3 | ??- | ??17.6 |
| DBA (part) | ??- | ??- | ??- | ??- | ??- | ??- | ??21 | ??- |
| BG (part) | ??- | ??4.5 | ??18 | ??- | ??- | ??- | ??- | ??- |
| HG (part) | ??- | ??- | ??- | ??- | ??- | ??- | ??42 | ??- |
| MPD (part) | ??- | ??- | ??- | ??- | ??11.9 | ??- | ??- | ??- |
| HDI (part) | ??242 | ??242 | ??- | ??244 | ??244 | ??307 | ??214 | ??244 |
| Hydrogenation MDI (part) | ??- | ??- | ??490 | ??- | ??- | ??- | ??- | ??- |
| THF (part) | ??217 | ??217 | ??238 | ??209 | ??227 | ??223 | ??277 | ??218 |
| Stablizer I (part) | ??2.5 | ??2.5 | ??3.1 | ??2.4 | ??2.4 | ??2.7 | ??3.1 | ??2.6 |
| Titanium dioxide (part) | ??15.3 | ??12.6 | ??15.3 | ??12.2 | ??15.2 | ??13.3 | ??15.7 | ??12.8 |
| Up?No. | ??Up1 | ??Up2 | ??Up3 | ??Up4 | ??Up5 | ??Up6 | ??Up7 | ??Up8 |
| NCO content (%) | ??2.2 | ??2.2 | ??4.2 | ??2.3 | ??2.2 | ??4.3 | ??0.9 | ??2.2 |
Preparation example 9
The preparation of the MEK ketimine compound of diamines.
Diamines and excessive MEK (molar weight is 4 times of diamines) refluxed 24 hours at 80 ℃, and the water that generates is expelled to outside the system.Under reduced pressure, unreacted MEK is removed then, obtain ketoimine I-III, i.e. the MEK ketimine compound.
Preparation example 10～14 and comparative preparation example 1～3
In reaction vessel, according to the scheme in the table 2 (weight part is represented with part in table), pack into Up and ketoimine, add the aqueous solution of 340 weight parts of the dispersion agent I that is dissolved with 1.3 weight parts then, then gained solution was mixed one minute under 900rpm with decollator I.Mixture transferred to be furnished with thermometer, in the reaction vessel of agitator and nitrogen flushing pipe,, the gained mixing solutions stirred 10 hours at 50 ℃ with nitrogen exchange air wherein.After reaction is finished,, obtain urethane resin powder (F1～F8) with solution filtering separation and dry.
The Mn of the resin of gained, STi (℃), Δ ST (℃), hard segment content (calculated value) (weight %), urea group content (weight %), aromatic nucleus content (weight %) and the equal particle diameter of body (μ m) be as shown in table 2.
Table 2
| Preparation example | The comparative preparation example | |||||||
| ????10 | ????11 | ????12 | ????13 | ????14 | ????1 | ????2 | ????3 | |
| Up No. (part) | ????Up1 ????100 | ????Up2 ????100 | ????Up3 ????100 | ????Up4 ????100 | ????Up5 ????100 | ????Up6 ????100 | ????Up7 ????100 | ????Up8 ????100 |
| Ketoimine No. (part) | ????I ????5.6 | ????I ????5.6 | ????II ????16.9 | ????I ????5.8 | ????I ????5.6 | ????I ????11.1 | ????I ????2.2 | ????III ????5.7 |
| Resin No. | ????F1 | ????F2 | ????F3 | ????F4 | ????F5 | ????F6 | ????F7 | ????F8 |
| Mn×1000 | ????25 | ????23 | ????26 | ????24 | ????24 | ????25 | ????26 | ????24 |
| STi | ????161 | ????140 | ????172 | ????170 | ????160 | ????219 | ????118 | ????89 |
| ΔST | ????19 | ????20 | ????27 | ????25 | ????27 | ????37 | ????6 | ????52 |
| Hard segment content | ????22.3 | ????22.7 | ????45.7 | ????23.4 | ????23.3 | ????29.2 | ????17.4 | ????23.7 |
| Urea group content | ????3.3 | ????3.3 | ????5.7 | ????3.5 | ????3.3 | ????6.3 | ????1.9 | ????3.3 |
| Aromatic nucleus content | ????8.0 | ????0 | ????0 | ????17.5 | ????0 | ????14.2 | ????0 | ????7.9 |
| The equal particle diameter of body | ????151 | ????150 | ????150 | ????154 | ????152 | ????150 | ????153 | ????154 |
Embodiment 1～3 and 5 and comparative example 1～4
With the softening agent I of the toner shown in the table 3 of 100 weight parts, 15 weight parts with as X22-3710 (the carboxy-modified organopolysiloxane of 0.05 weight part of inner pattern releasing agent applicable, produce by SHIN-ETSU HANTOTAI's chemical industry (strain)) the Henschel mixing tank of packing into (Henschel Mixer), and under 200rpm, raw material was mixed one minute.In comparative example 4, the commercially available polyvinyl chloride powder (called after S-130) [Tg:-60 ℃, STi:160 ℃, Δ ST:20 ℃] that is used for slush molding replaces polyurethane powder, obtains material S9.
After the mixing, mixture is cooled to 40 ℃ then 80 ℃ of slakings 2 hours.Obtain slush molding with material (S1～S3, and S5～S9), equal particle diameter of its body (μ m) and particle diameter are shown in Table 3 smaller or equal to the fine particle content (weight part) of 75 μ m to the anti-hard caking agent I that wherein adds 1 weight part.
Embodiment 4
With shown in the 100 weight part tables 3 toner, the softening agent II of 15 weight parts and (the carboxy-modified organopolysiloxane of the X22-3710 as inner pattern releasing agent applicable of 0.05 weight part, produce by SHIN-ETSU HANTOTAI's chemical industry (strain)) the Henschel mixing tank of packing into, and under 200rpm, raw material was mixed one minute.
After the mixing, mixture is cooled to 40 ℃ then 80 ℃ of slakings 2 hours.Obtain slush molding material (S4) to the anti-hard caking agent I that wherein adds 1 weight part, equal particle diameter of its body (μ m) and particle diameter are as shown in table 3 smaller or equal to the fine particle content (weight part) of 75 μ m.
Mensuration is with the homogenizing time (leveling time) (second) of this material S1～S8 that obtains.
Sumimold FA[is lived ore deposit lubricant (strain)] spray in the mold, and mold is heated to 250 ℃, make slush molding (S1～S9) contacts 30 seconds and make its heat fusing with mold after, the material that obtains at room temperature be placed 1 minute and make the molding sheet with water cooling with material.Detect the melting characteristic and the thermotolerance of the molding sheet that adopts material S1～S9 preparation.Outcome record is in table 3.
In addition, put into the molding sheet of S1～S9 that mold obtains for each sheet, adding a kind of urethane foam forms component [(number-average molecular weight is 5 by the EO polypropylene glycol triol thin slice of 95 weight parts, 000), the trolamine of 5 weight parts, 2.5 weight parts waters, 1 weight part triethylamine and 61.5 weight part polymeric MDIs are formed], and make its foaming and tightly adhere to, thereby obtain having S1～the urethane foam moulding bodies of S9 outer shell.These moulding bodies 120 ℃ of thermal treatments 500 hours, are removed urethane foam in the drying by circulating air device then from moulding bodies.To before each thermal treatment and thermal treatment after molding sheet (outer shell) carry out performance test (Tg and crooked experiment).In addition, measure its shrink grading simultaneously.The result is as shown in table 3.
Table 3
| Embodiment | Comparative example | |||||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????1 | ????2 | ????3 | ????4 | ||
| Resin No. | ????F1 | ????F2 | ????F3 | ????F4 | ????F5 | ????F6 | ????F7 | ????F8 | ????S-130 | |
| Material No. | ????S1 | ????S2 | ????S3 | ????S4 | ????S5 | ????S6 | ????S7 | ????S8 | ????S9 | |
| The equal particle diameter of body | ????159 | ????158 | ????161 | ????158 | ????157 | ????158 | ????160 | ????161 | ????140 | |
| Fine particle content (%) | ????13 | ????14 | ????15 | ????14 | ????13 | ????14 | ????13 | ????13 | ????3 | |
| The homogenizing time | ????85 | ????68 | ????78 | ????78 | ????87 | ????≥600 | ????38 | ????97 | ????- | |
| Melting behaviour | 4 grades | 5 grades | 4 grades | 4 grades | 4 grades | 1 grade | 5 grades | 4 grades | ????- | |
| Thermotolerance | ????◎ | ????◎ | ????○ | ????◎ | ????○ | ????-* | ????× | ????× | ????- | |
| Tg(℃) | Before the thermal treatment | ????-37 | ????-49 | ????-49 | ????-45 | ????-46 | ????-27 | ????-49 | ????-38 | ????-60 |
| After the thermal treatment | ????-44 | ????-55 | ????-55 | ????-38 | ????-52 | ????-33 | ????-55 | ????-45 | ????-30 | |
| Crooked experiment | Before the thermal treatment | ????○ | ????○ | ????○ | ????○ | ????○ | ????× | ????○ | ????○ | ????○ |
| After the thermal treatment | ????○ | ????○ | ????○ | ????○ | ????○ | ????× | ????○ | ????○ | ????× | |
| Shrink grading (%) | ????0 | ????0 | ????0 | ????0 | ????0 | ????0 | ????0 | ????0 | ????5 | |
＜measuring method 〉
(1) measuring method of STi and STe
It is the film of 800～1200 μ m that the thermal plastic urethane toner formed thickness in 2 minutes at 190 ℃ of pressing molds.Use thermomechanical analysis device [Thermoflex TMA 8140] and [TAS 100] (Rigaku Denki Co., Ltd's production) to adopt thermomechanical analysis osmose process (hereinafter being expressed as TMA) to measure the STi and the Ste of these film samples.In the TMA chart, according to [JIS K7121-1987, p-5, Fig. 3, stage change], adopt the method same to measure STi (Tig with inferring the vitrifying starting temperature, ℃) and use the method same with inferring the vitrifying final temperature to measure Ste (Teg, ℃) (the TMA measuring condition: temperature rise rate is 5 ℃/min, loading capacity 5g, probe diameter is 0.5mm).Synthetic toner (F1) and TMA figure (F8) are illustrated in accompanying drawing 1 and 2.The temperature at place, the point of crossing of the tangent line (dotted line) of TMA curve (solid line) is corresponding to STi and STe in the accompanying drawing.ΔST＝STe-STi。
(2) melting behaviour
The molded side of molding sheet and the melting condition at its back side are estimated, and it is estimated according to following 5 ranks.
5 grades: molded side is melted fully.Evenly melt at the back side, smooth, smooth.
4 grades: molded side is melted fully.Evenly melt at the back side, but slight unfairness is arranged.
3 grades: molded side is melted fully.The part back side is residual the powder that does not melt.
2 grades: molded side is melted insufficient.The back side is residual many powder that do not melt.
1 grade: material does not melt at all.
(3) the homogenizing time
A polishing steel plate is placed on and is heated to 190 ℃ on the hot plate, drip the sample powder of last 10～14mg then with miniature spatula.The area of drippage is 4mm * 8mm.Sample powder reaches and melts fully and the needed time of smooth surface on the measurement polishing steel plate.
(4) thermotolerance
The molding sheet was placed 24 hours at 130 ℃ in circular dryer, and its state carries out visual assessment: ◎ according to following 3 ranks: do not change; Zero: gauffer does not flow, but light is arranged; *: gauffer flows and light is arranged.
(5)Tg
Use the DSC[model: DSC220C, manufacturers: Seiko electronic industry (strain)] in nitrogen, measure Tg.In the preproduction phase of measuring stage, temperature is elevated to 100 ℃ from room temperature and is reduced to-100 ℃ then.Again when-100 ℃ are elevated to 100 ℃, measure Tg with 20 ℃/minute speed in temperature.
(6) number-average molecular weight
Adopt gel permeation chromatography [model: HLC-8220, manufacturers: eastern Cao (strain)] to use N, dinethylformamide comes determining molecular weight as solvent.
(7) the equal particle diameter of body
The equal particle diameter of body refers to can be with the undersized particle size values of 50% particle.Adopt MicrotrackHRA particle-size analyzer 9320-X100 (producing) to measure by day machine dress (strain).
(8) crooked experiment
The molding sheet was placed 1 hour at-35 ℃, it is bent to 180 ° then, whether observation occurs breaking.
Appearance is broken: *
Do not break: zero
(9) shrink grading
On 200mm * 200mm slice surfaces at the reference line that draws abreast apart from the inboard of every sideline 10mm.At least accurately measure two spacings between the parallel lines in three or more places, with the length of estimating each and the mean value of width.These values are as original size.Thin slice is put into 110 ℃ baking oven, and kept 800 hours.Thin slice is taken out from baking oven, at room temperature placed 24 hours.And then measurement size and with the degree of following formula evaluate shrinkage.
Shrink grading (%)=100 * [size (mm) after original size (mm)-heating]/original size (mm)
Industrial applicibility
The polyurethane type resin material that the present invention is used for slush molding has following effect:
1, this material has good heat resistance heat-resisting quantity, and its surface can be not shinny after test, and lip-deep gauffer can not flow.
2, because this material has good hot melt property, can not occur irregular paintedly, so moulding bodies has good outward appearance.
3, powder has good longer-term storage stability.
4, can make the moulding bodies with excellent abrasive resistance.
5, TPU of the present invention, that is, the material that is used for molding instrument face plate shell has the interior glass transition temperature of-60 ℃～-35 ℃ scopes. Even Tg still can remain in this scope after heat treatment. In addition, can not break even adopt the molded moulding bodies of material of the present invention under cryogenic conditions, to carry out crooked experiment yet. And, thermal contraction can not occur, therefore can accurately keep its size.
6, therefore instrument face plate shell of the present invention can breach not occur in other parts except tear line owing to used above-mentioned material.
7, preparation method of the present invention is suitable for adopting previous materials to prepare above-mentioned shell of the present invention.
8, in addition, when using inner pattern releasing agent applicable (C) as the moulding reagent of slush molding polyurethane outer:
(1) polyurethane outer and mold have good stripping feature.
(2) adhesivity between polyurethane outer and the polyurethane foam there is not detrimentally affect.
(3) shell has the good anti-diffusion of coloring matter, so moulded product can not sacrificed outward appearance.
Owing to possess above-mentioned effect, adopt moulding bodies and the slush molding shell of slush molding of the present invention with the automotive interior use of material preparation, be very useful as multiple automotive interior material, comprise instrument panel and architrave.In addition, this shell can be used for preparing the instrument panel that integrally has an air bag door part, and the tear line that wherein is used to tear is not exposed to the design surface of instrument panel air bag door part.In addition, the moulding bodies that also can be used for preparing other comprises that indoor furniture is as sofa with shell etc.
Claims (21)
1. the material that is used for slush molding, it contains TPU(Thermoplastic polyurethanes) (A); Adopting the initial softening temperature and the difference between the end softening temperature of the described resin (A) of thermomechanical analysis osmose process mensuration is 0～30 ℃, and the initial softening temperature of described resin (A) is 135～200 ℃.
2. material as claimed in claim 1, wherein said resin (A) is a urethane resin, described urethane resin contains hard segment (A1) and soft chain segment (A2); The number-average molecular weight of described hard segment comprises at least a being selected from by the vulcabond with symmetrical structure (a1) in 200 to 2000 scopes, have the material in the lower molecular weight diamines (a2) of symmetrical structure and the group that low molecular weight diols (a3) is formed; It is 500～5000 high molecular weight diol (a4) that described soft chain segment (A2) contains number-average molecular weight; The content of hard segment is 5 weight %～50 weight % in the described resin, and the content of aromatic nucleus is smaller or equal to 35 weight % in the described resin, and the content of aromatic nucleus and urea group satisfies following equation (i):
-0.1x+2.5≤y≤-0.1x+6????(i)
Wherein, x represents the weight percentage of aromatic nucleus in the resin (A), and y is the weight percentage of urea group in the resin (A).
3. material as claimed in claim 2, wherein, the content x of aromatic nucleus is 5 weight %～25 weight % in the described resin (A), and wherein, the content y of the content of aromatic nucleus and urea group satisfies following relationship (i '):
-0.1x+3≤y≤-0.1x+5????(i′)。
4. as claim 2 or 3 described materials, wherein, the number-average molecular weight of described hard segment is 200～2000, comprise at least a being selected from, have the lower molecular weight diamines (a2) of symmetrical structure and have material in the group that the low molecular weight diols (a3 ') of symmetrical structure formed by the vulcabond with symmetrical structure (a1).
5. as any described material in the claim 2～4, wherein, described diamines (a2) is for being selected from the straight chain alkylene diamines with 2～18 carbon atoms, two (2-amino-ethyl) carbonic ether, 4,4 '-dicyclohexyl methyl hydride diamines, hexanaphthene-1,4-diamines, p-Xylol diamines, α, α, α ', at least a material in the group that α '-tetramethyl-Asia 3,5-dimethylphenyl diamines and 4,4 '-diamines-ditan is formed.
6. as any described material in the claim 2～5, wherein, described vulcabond (a1) is for being selected from 1, the 2-ethylidene diisocyanate, 1, the 4-tetramethylene diisocyanate, 1, the 6-hexamethylene diisocyanate, 1,12-ten dimethylene diisocyanates, two (2-isocyanic acid ethyl) carbonic ether, 4,4 '-dicyclohexyl methane diisocyanate, hexanaphthene-1, the 4-vulcabond, the p-Xylol vulcabond, α, α, α ', at least a a kind of material in the group that α '-tetramethyl-Asia dimethyl benzene group diisocyanate and 4,4 '-diphenylmethanediisocyanate is formed.
7. as any described material in the claim 2～6, wherein, the residue of described diamines (a2) has the identical structure of residue with described vulcabond (a1).
8. as any described material in the claim 2～7, wherein, described glycol (a3) is with any one expression in following general formula (1), (2) and (3):
HO(CH
2)
m-(Q
1)
p-(CH
2)
mOH???????????????????????????????????(1)
H(OCH
2CH
2)
nO-Q
2-O(CH
2CH
2O)
nH?????????????????????????????(2)
H(OCH
2CH
2CH
2CH
2)
kO-Q
2-O(CH
2CH
2CH
2CH
2O)
kH???????????(3)
Wherein, in formula (1), Q
1Be methylene radical, 1,4-cyclohexylidene or 1,4-phenylene; P is 0 or 1; M is 0 or 1～6 integer, if wherein p is 0 or Q
1Be 1, the 4-phenylene, m is 1～6 so; In formula (2) and formula (3), Q
2Be bisphenol residue or 1, the 4-phenylene; N is an integer 1～3; And in formula (3), k is 1 or 2, works as Q
2When being the residue of bis-phenol, k is 1.
9. as any described material in the claim 1～8, wherein, contain described resin (A) and softening agent (B) in the described material; Described material is the powder with equal particle diameter of body of 100～500 μ m, and particle diameter smaller or equal to the content of the powder particle of 75 μ m smaller or equal to 20 weight %.
10. material as claimed in claim 9, wherein, described softening agent is the phosphoric acid ester by following general formula (5) expression:
Wherein, R is the monovalence alkyl with 1～10 carbon atom, and described alkyl selectivity has halogen to replace, a plurality of R are identical or different, R ' is the divalent organic group with 2～15 carbon atoms, and described organic group can selectivity have halogen to replace, and q is 1～6 integer.
11. material as claimed in claim 10, wherein, the R in the general formula (5) is phenyl, alkyl phenyl or the phenyl that the halogen replacement is arranged, and R ' is the group of following general formula (6) expression:
-Ph′-(A-Ph′)
P-??????????(6)
Wherein, Ph ' represents 1, and 4-phenylene, p are 0 or 1, and A is Direct Bonding, methylene radical, isopropylidene or SO.
12. material as claimed in claim 9, wherein, described softening agent (B) is the fragrant monocarboxylic ester of polyalkylene glycol.
13. as any described material in the claim 1～12, it further contains:
The inner pattern releasing agent applicable (C) that is used for the surface modes moulding material of slush molding urethane, comprise: be selected from (f) and contain compound in the group that the siloxanes through modification of a polar group (c) forms by the phosphoric acid ester (salt) of the fluorine modification of general formula (11) expression, the described siloxanes through modification that contains a polar group (c) is selected from the carboxy-modified organopolysiloxane (c1) by general formula (8) expression, the epoxide modified organopolysiloxane (c2) of general formula (9) expression, and at least a in the group formed of the organopolysiloxane (c3) of the ether modification of general formula (10) expression;
(R
f-D-O)
rP(＝O)(OH)
3-r???????????????????(11)
In (10), Q is usefulness-R at general formula (8)
2The carboxyl that COOH represents; X is for being expressed as
Or
Epoxy group(ing), Z is expressed as-C
3H
6O (C
2H
4O)
p-(C
3H
6O)
qR
3Polyether group; R
1It is alkyl with 1～4 carbon atom; R
2It is alkylidene group with 1～4 carbon atom; R
3Be H, have the alkyl or an ethanoyl of 1～4 carbon atom; Me is a methyl; A, b and c are respectively 0 or 1 separately, and if a=1 and b=1 then c=0; M and n be meet (m+n) be 10～200 and n/ (m+n) be 0～0.5 numeral; P and q be meet (p+q) be 3～100 and p/ (p+q) be 0～0.6 numeral; In general formula (11), R
fIt is perfluoroalkyl with 4～20 carbon atoms; D is by-CH
2CH (E) C
sH
2s-or-SO
2N (R
4) C
tH
2tThe divalent organic group of-expression, wherein E is H, CH
3, C
2H
5, Cl or OR
5, R
5Be H, CH
3, C
2H
5, COC
2H
3, COC
2H
5, or CH
2COOH or its salt; S is 0～4 integer; R
4It is alkyl with 1～4 carbon atom; T is 1～4 integer; R is integer 2 or 3.
14. material as claimed in claim 13, wherein, inner pattern releasing agent applicable (C) contains:
Be selected from a kind of material in the group of being formed by the organopolysiloxane (c3) of carboxyl acid modified organopolysiloxane (c1) and ether modification,
Be selected from least a composition of (f) forming with phosphoric acid ester (salt) the fluorine modification in the organopolysiloxane (c3) of carboxyl acid modified organopolysiloxane (c1), epoxide modified organopolysiloxane (c2) and ether modification, or
The composition that the organopolysiloxane (c3) of carboxyl acid modified organopolysiloxane (c1) and ether modification is formed.
15. as any described material in the claim 1～14, wherein, described material further comprises additive (D).
16. the slush molding product, described slush molding product are prepared through hot-moulded with material by any described slush molding in the claim 1～15.
17. automotive interior slush molding shell, described slush molding shell is by preparing through hot-moulded with material as any described slush molding in the claim 1～15.
18. the automotive interior material wherein contains slush molding shell as claimed in claim 17.
19. as any described slush molding material in the claim 1～15, wherein, the second-order transition temperature of described resin (A) is-60 ℃～-35 ℃, this material can be used for molding automobile instrument panel enclosure, this shell integrally has an air bag door part, and the tear line of wherein tearing usefulness is not exposed on the design surface.
20. the automobile instrument panel enclosure, described automobile instrument panel enclosure is moldedly formed with the material molding by as claimed in claim 19, and this shell integrally has an air bag door part, and the tear line of wherein tearing usefulness is not exposed on the design surface.
21. preparation integrally has the method for the automobile instrument panel of an air bag door part, the tear line of wherein tearing usefulness is not exposed on the design surface, comprising:
Hot-moulded molding material as claimed in claim 19, and
In described hot-moulded process, on moulded product, be formed for tear line that the air bag door part is torn, make tear line not be exposed on the design surface.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP108466/2002 | 2002-04-10 | ||
| JP2002108466A JP2003300428A (en) | 2002-04-10 | 2002-04-10 | Material for molding instrument panel skin having air bag door part |
| JP2002108467 | 2002-04-10 | ||
| JP108467/2002 | 2002-04-10 | ||
| JP226743/2002 | 2002-08-02 | ||
| JP2002226743A JP3981310B2 (en) | 2002-08-02 | 2002-08-02 | Internal mold release agent for slush molded polyurethane skin forming agent |
| JP99710/2003 | 2003-04-02 | ||
| JP2003099710A JP2004002786A (en) | 2002-04-10 | 2003-04-02 | Polyurethane resin as slush casting material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1646590A true CN1646590A (en) | 2005-07-27 |
| CN1301281C CN1301281C (en) | 2007-02-21 |
Family
ID=28795110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038081083A Expired - Lifetime CN1301281C (en) | 2002-04-10 | 2003-04-08 | Polyurethane resin based slush molding material |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US7405257B2 (en) |
| EP (1) | EP1493763A4 (en) |
| KR (1) | KR100594616B1 (en) |
| CN (1) | CN1301281C (en) |
| WO (1) | WO2003085023A1 (en) |
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| CN103331411A (en) * | 2013-05-29 | 2013-10-02 | 上海星杜新材料科技有限公司 | Efficient, lossless, precision molding demoulding addictive for pressure casting and preparation method thereof |
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| CN108912299A (en) * | 2018-08-01 | 2018-11-30 | 浙江华峰热塑性聚氨酯有限公司 | Roll grade high-temperature-resistant thermoplastic polyurethane elastomer and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101675111B (en) * | 2007-03-01 | 2012-06-13 | 三洋化成工业株式会社 | Resin powder composition for slush molding and molded articles |
| CN101784609B (en) * | 2007-08-10 | 2012-07-04 | 拜尔材料科学有限公司 | Thermoplastic aliphatic urethane/urea molding compositions |
| US9644289B2 (en) | 2011-03-14 | 2017-05-09 | Asahi Kasei Fibers Corporation | Polyurethane elastic fiber |
| CN103331411A (en) * | 2013-05-29 | 2013-10-02 | 上海星杜新材料科技有限公司 | Efficient, lossless, precision molding demoulding addictive for pressure casting and preparation method thereof |
| CN103331411B (en) * | 2013-05-29 | 2015-05-20 | 上海星杜新材料科技有限公司 | Efficient, lossless, precision molding demoulding addictive for pressure casting and preparation method thereof |
| CN107249841A (en) * | 2015-02-20 | 2017-10-13 | 信越化学工业株式会社 | Tyre capsule releasing agent, tyre capsule and air tyre |
| CN107249841B (en) * | 2015-02-20 | 2019-11-01 | 信越化学工业株式会社 | Tyre capsule release agent, tyre capsule and air tyre |
| CN108912299A (en) * | 2018-08-01 | 2018-11-30 | 浙江华峰热塑性聚氨酯有限公司 | Roll grade high-temperature-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN108912299B (en) * | 2018-08-01 | 2021-01-05 | 浙江华峰热塑性聚氨酯有限公司 | Calendering-grade high-temperature-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN113968958A (en) * | 2021-11-26 | 2022-01-25 | 广东富强科技股份有限公司 | Polyurethane and preparation method and application thereof |
| CN113968958B (en) * | 2021-11-26 | 2023-11-21 | 广东富强科技股份有限公司 | Polyurethane and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1493763A4 (en) | 2012-12-19 |
| EP1493763A1 (en) | 2005-01-05 |
| KR20050002881A (en) | 2005-01-10 |
| US7405257B2 (en) | 2008-07-29 |
| WO2003085023A1 (en) | 2003-10-16 |
| KR100594616B1 (en) | 2006-06-30 |
| CN1301281C (en) | 2007-02-21 |
| US20060045996A1 (en) | 2006-03-02 |
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